Aromatic polysulfites

ABSTRACT

The disclosure describes novel compounds, the bischlorosulfinate of di-(monohydroxyaryl)alkanes, and a novel method for producing aromatic polysulfites from said bischlorosulfinates by heating the bis-chlorosulfinate under reduced pressure whereby the bis-chlorosulfinate undergoes selfpolymerization to form an aromatic polysulfite.

United States Patent Hull [ 51 Oct. 17, 1972 [54] AROMATIC POLYSULFITES [72] Inventor: Colin G. Hull, San Francisco, Calif.

[73] Assigne'e: Shell Oil Company, New York, NY.

[22] Filed: Sept. 19, 19 69 211 Appl. No.: 859,557

52 user ..260/456 P,260/49 51 int. c|.....'- ..C07c 143/68 [58] Field of Search ..260/456 R, 456 P [56] I References Cited UNITED STATES PATENTS 2,624,750 1/1953 Pechukas ..260/456 R X OTHER PUBLICATIONS Chemical Abstracts 56: 5869c (1962). I

. Primary Examiner-Leon Zitver Assistant Examiner-Leo R'. De Crescent'e Attorneyr-loseph W. Brown and Martin A. Voet 57] ABSTRACT 4 Claims, No Drawings Once the bis-chlorosulfinate is made, aromatic polysulfites may be produced 'by simply heating the bischlorosulfinate at moderate temperatures. 'By moderate temperatures is meant above about 125 C and preferably between about 140 and 160 C. While the reaction may be run. at atmospheric pressure, a

. somewhat reduced pressure facilitates the reaction.

Patent No. 1,213,612. The present invention relates to novel compounds, namely the bis-chlorosulfinates of di-(Monohydroxyaryl)alkanes and a novel method for producing aromatic polysulfites from said his chlorosulfinates.

The present invention thus comprises compounds of i the formula I x wherein each R is selected from the group consisting of phenylene, halo-substituted p'henylene and alkylsubstituted phenylene radicals, and X and-Y'are each selected from the group consisting of' hydrogen,-

h r c rbo radisals; free; f m a rzha m tion and of radicals-which together and with the adjoining carbon atom form a'cycloalkane radical, the total number of carbon atoms in X and Y being up producing aromatic polysulfites comprising heating under reduced pressure .a compound having the formuwherein each 'Rjis selected from the group consisting of phenylene, halo-substituted phenylene and alkylsubstituted phenylene radicals and X and Y are each selected from the group-consisting of hydrogen,

hydrocarbon radicals free from aliphatic unsaturation and of radicals which together and with the adjoining carbon atom' .form a' cycloalkane radical, the total number of carbon atoms in X a r 1d Y being.up to whereby the compound undergoes self-polymerizaton o 95, 1! !QIQQ liQBQlEP filE.

The process for producing the new compounds'cohiprises reacting the di-(monohydroxyaryDalkanes with thionyl'chloride in a suitable solvent under an inert gas at low temperatures. Suitable solvents are those solvents which are non-reactive with thionyl chloride,

such as hydrocarbon solvents, halo-substituted hydrocarbon solvents, ether solvents and aromatic solvents. Specific solvents which are suitable are, for example, diethyl ether, dichloromethane, cyclohexane, tetrahydrofuran and carbon tetrachloride. By low temperatures are meant temperatures in the range of about 0 to 10 C and preferably about 5 C. The reaction proceeds well at atmospheric pressure but may be carried out under pressure if desired.- The resulting new compounds'may be recovered by simply removing the solvent by any convenient means, such as, for example, evaporation. Since the resulting compounds hydrolyze relatively easily, care must be taken in storage of the material.

The present invention also relates to a method of Suitable di-(monohydroiryarynalkanes are for example (4,4 '-diliydroxydiphenyDmetharie, 2,2-(4,'4'- dihydroxy-diphenyl)propane (Bisphenol A), 1,1 -(4,4'- dihydroxy-diphenyl)chlohexane, 1', l 4,4 -dihydroxy- '3,3-dimethyldiphenyl)butane, (boiling point; 185

-l88C 'under 0.5 mm mercury gauge) 2,2- (2,2'- dihydroxy-4,4 -ditert-butyl-diphenyl)propane or 1,1"- (4,4'-dihydroxydiphenyl)-l -phenyl-ethane,', furthermore methane derivatives which carry besides two :hydroxyaryl groups an alkyl residue, with at least two carbon atoms and a second alkyl residu'ewithone or more carbon atoms, such as 2,2-(4,4'-dihyd roxydiphenyl)butane,' .2,2-('4,4'-dihydroxy-diphenyl)pentane (melting point l49 l.50C), 3,3-(4,4-dihydroxydiphenyl)pentane, 2,2-(.4',4'-dihydroxydiphenyl)hexane, 3,3-(4,4-dihydro ry-diphenyl)hexane, 2,2-(4,4-'- dihydroxydiphenyl)-4-methyl-pentane (melting point 15 1- l 5 2C), 2,2-(4,4 '-,dihydroxydiphen'yl)heptane (boiling point 198-200C under 0.3mm mercury gauge), (4,4'- dihydroxy-diphenyl)heptane (melting point l48- l49C), or 2,2- (4,4'-dihydroxydiphenyl)-tridecane. Suitable di-('monohydroxyaryl)alkanes, the two aryl residues'of which are different, arefor example 2,2-(4',4 '-dihydroxy-3methyl-diphenyl)propane and 2,2- (4,4' dihydroxy 3-methyl-3 -isopropyldiphenyl)butane. Suitable di-(monohydroxyaryl)alkanes, the aryl residues of which carry halogen atoms, are for instance 2,2-( 3 ,5 ,3 ',5 '-tetra-chloro-4,4 '-dihydorxydiphenyl)propane, 2,2-(3,5,3,' 5-tetrabromo-4,4- dihydroxy-diphenyl) propane, (3,3 '-dichloro-4,4'-

' dihydroxy-diphenyl)methane and 2,2'-dihydroxy-5,5'-

difluoro-diphenyl-methane. Suitable di-(monohydroxyaryl)alkanes,. the alkyl residue of which linking the two benzene rings is substituted by. an aryl residue, are for instance (4,4 '-dihydroxy-diphenyl)phenyl-methane and l l -(4,4-dihydroxy-diphenyl) l -phenyl-ethane.

EXAMPLES The following examples illustrate particularembodiments of the present invention, including the preferred embodiments. The invention is not to be interpreted as being limited by the illustrative examples, which are presented only to facilitate a better understanding thereof. Unless otherwise specified, parts is parts by weight.

EXAMPLE I i 1 Preparation of the bis-chlorosulfinate of Bisphenol A a t i t as... V 0H5 57.1 parts (0.25mol) of Bisphenol A [2,2-bis(4- hydroxyphenyl)propane] was dissolved in parts by volume of diethyl ether. parts of thionyl chloride and 20 ml of diethyl ether were placed in a reaction flask and cooled to 5C in an ice/salt bath. The Bisphenol A/diethyl ether solution was then added over 40 minutes with stirring under C0,. The cooling bath was removed allowing the reaction product to come to room temperature. 85.3 parts of a straw colored 1 viscous liquid was recovered. The following tests indicated that the recovered material was the bischlorosulfinate of BisphenolA. I

Chemical analysis of the recovered compound compared. to the formula of the bis-chlorosulfinate of Bisphenol A was as follows:

Analysis of Analysis of Recovered Compound (1:)

c 45.8 v 48.3 n 3.6 3.9--

s 16.3 14.8 C 18.0 2 .l7.'l

Infrared Spectrataken of the recovered'compound showed wavelengths of S=O at-1,230c'rn'l. In'addition,

" no trace of -H stretch was fou'nd'indicating that the compound contained no free Bisphenol A.

Additionally, 5 .2608g I of the compound was hydrolyzed and yielded 2.9977g Bisphenol as follows:

MEXAMPLVEII Examplel is.repeatedexceptthat l,l'-(4,4-dihy'd'rox- A y-diphenyl)-cyclohexane is used in place of Bisphenol A'R'elated results are obtained.

EXAMPLE II-I Example. I-is repeated except thatv 2,2-(4,4

dihydorxy-3'-methyldiphenyl)propane is used in place of Bisphenol A. Related results are obtained.

"EXAMPLE IV Example l is repeated except that 2,2-(4,4'- dihydroxy-diphenyl)-butane is used in place of Bisphenol A-.'Related resultsare obtained.

' EXAMPLE V Preparation of Bisphenol A polysulfite OH: I

iQiQ i 10 parts of the bis-chlorosulfinate. of Bisphenol A A (Theoretical Bisphenol A is 3.053 I g) The reaction was produced in Example I was placed 'in a ml 2-neck flask. The flask was slowly heated in an oil bath to 155C under reduced pressure with stirring and held at the temperature for several hours. Thionyl chloride was found to be releasedduring the reaction. The reaction product was worked up in a high shear blender with methanol to yield a tan, fluffy polymer. Chemical analysis of the polymer indicated that it was the-polysulfite 4 had a molecular weight between about 1,000 and 2000 and thus n was between about .4and

TABLE I ANALYSIS OF POLYMER RECOVERED IN EXAMPLE V' Theory Actually Found (17) Iclaim as my invention: A I 1. A process for producing aromatic polysulfites comprising heating under reduced pressure and at a temperature above about 12$."C a compound having' the formula wherein each Rflis selected from group consistingof phenylene, halo-substituted phenylene and alkyl-sub being up to 12, whereby the compound undergoes self- 40- polymerization. v

2. A process for producing aromatic polysulfites comprising heating under reduced pressure and at a temperature above about 125C a compound having the formula wherein each R is phenylene and and Y are each alkyl radicals, the total number of carbon atoms in X and Y being up to six, whereby the compound undergoes selfpolymerization.

3. A process ,for producing thev polysulfite of Bisphenol A comprising heating under reducedpresof Bisphenol A (asindicated at Table I)..The polymer sure and at a temperature above about Cthe bis chlorosulfinate of Bisphenol A.

4. A process as inclaim 2 wherein the temperature during heating ranges between about and C.

* IF III 

2. A process for producing aromatic polysulfites comprising heating under reduced pressure and at a temperature above about 125*C a compound having the formula wherein each R is phenylene and and Y are each alkyl radicals, the total number of carbon atoms in X and Y being up to six, whereby the compound undergoes self-polymerization.
 3. A process for producing the polysulfite of Bisphenol A comprising heating under reduced pressure and at a temperature above about 125*C the bis chlorosulfinate of Bisphenol A.
 4. A process as in claim 2 wherein the temperature during heating ranges between about 135 and 170*C. 